Amine salts of anthraquinone sulfonic acid compounds



AMINE SALTS F ANT HRAQUINONE SULFONIC ACID COMPOUNDS Karl Maier and Julius Eisele, Ludwigshafen (Rhine), and

Wilhelm Federkiel, Frankenthal, Pfalz, Germany, assignors to Badische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen (Rhine), Germany No Drawing. Application January 20, 1956 Serial No. 560,279

Claims priority, application Germany January 22, 1955 l 5 Claims. (Cl. 260-367) This invention relates to dyestufis of the anthraquinone series and in particular to dyestulfs which are salts resulting from the reaction between sulfonic acids of the anthraquinone series and organic nitrogen bases.

We have found that very' valuable dyestufis are obtained by neutralizing sulfonic acids of the anthraquinone series having the general formula HEN NH-X-NH NH:

Ho s S0311 wherein X represents a bivalent organic radical derived from a bicyclic compound such as diphenylmethane or 2.2-diphenylpropane joined in the pand p'-positions of the benzene nuclei with the NH-groups of the anthraquinone radicals, which may contain substantially neutral ring substituents such as lower alkyl or lower alkoxy groups or halogen atoms in their meta or ortho positions, with about the equivalent amount of organic nitrogenous monoor polyvalent bases. By the equivalent amount is meant two molecular base equivalents of the base for each molecular equivalent of anthraquinone derivative, having two sulfonic acid groups.

Sulfonic acids of the anthraquinoneseries represented by the above general formula can be prepared by known methods, for example by reaction of l-amino-4-bromantraquinoneQ-sulfonic acid with diamines, such as bis-(paminophenyD-methane or 2.2-bis-(p-aminophenyl)-propane, according to the process described in U.S. Patent No. 2,156,887.

Suitable monoor polyvalent nitrogenous bases for the neutralization of the sulfonic acids of the anthraquinone ttes Patent 0 series of the above mentioned general formula are polyamines, Such as 1.6-hexamethylene diamine or bis-(p- O NH:

m4 03H Hots I I 2,913,465 Patented Nov. 17, 1959 the free amines or with their salts, for example their hydrohalides, in aqueous or aqueous-alcoholic solutions, advantageously at elevated temperature, preferably 70 to 100 C. Neither component need be used in excess. When the alkali salts of the sulfonic acids are used, the reaction proceeds more rapidly than when the free sulfonic acids are used as the latter are but poorly soluble in water. The preferred practice in reacting the free amines with the alkali salts of the sulfonic acids is to neutralize the hydroxyl ions formed by the addition of corresponding amounts of acids, such as hydrochloric acid. When starting from the salts of the amines, for example the hydrochlorides and the alkali metal salts of the sulfonic acids the resultant reaction products are almost completely free fom the alkali salts which are products of the reaction.

The initial sulfonic acids of the anthraquinone series and their alkali metal salts are more or less soluble in water. On the contrary the final dyestulfs obtained according to this invention are difficultly soluble or insoluble in water. The dyestuffs obtained can in any case be purified by extracting them with boiling water. They dye both animal fibres, as for example wool or silk, and also fibres, foils or other shaped articles from polyamides, polyurethanes or casein, from neutral or weakly acid aqueous dispersions in good level shades which have good fastness properties, especially outstanding wet fastness properties. They are superior in their fastness properties to the initial sulfonic acids of the anthraquinone series which have not been reacted with amines, and, in addition, they have a clearer and more brilliant shade.

The following examples will further illustrate this invention but the invention is not restricted to these examples. The parts are parts by weight.

Example 1 5 parts of the sodium salt of the dyestuff obtained according to the said US. Patent No. 2,156,887 by condensing 2 mols of 1-amino-4-bromanthraquinone-2-sulfonic acid and 1 mol of bis-(p-aminophenyl)-methane are heated at to C. with 2.5 parts of bis-(p-dilmethylaminocyclohexyl)-methane in parts of a mixture of equal parts of methanol and water for about 2 hours while stirring on a waterbath. After distilling oil the alcohol and neutralizing with dilute hydrochloric acid, the precipitated reaction productis extracted several times with boiling water. 6 parts of an insoluble dyestuff are obtained which dyes, for example, wool and polyamide fibres greenish blue shades of good fastness properties, especially of outstanding wet fastness properties which are. superior to those of the dyeings obtained with the initial sulfonic acid which have not been reacted with an amine. The formula of the obtained dyestuff is:

HzN O where Me represents -a methyl group.

Example 2 5 parts of the initial dyestulf obtained by condensing 2 mols of 1-amino-4-bromanthraquinone-Z-sulfonic acid with one mol of bis-(p-aminophenyl)-methane are stirred in 50 parts of a mixture of equal parts of methanol and water with 2.5 parts of bis-(p-aminocyclohexyl)-methane A of which, for example on wool and polyamide fibres, show good fastness properties which are superior to those of the dyeings obtained with the initial sulfonic acid which have not been reacted with an amine.

The formula of the obtained dyestufi is:

O 171' Hz Half 03H Hogs- I h EN-omitt i-onir-Nn fibres greenish blue shades of good fastness properties, especially of outstanding wet fastncss properties which are superior to those of the dyeings obtained with the initial sulfonic acid which have not been reacted with an amine.

The formula of the obtained dyestufi is:

Example 5 5 parts of the dyestuff obtained by condensing 2 mols of 1-amino-4-bromanthraquinone-2-sulfonic acid and 1 mol of bis-(p-aminophenyl)-methane are dissolved in hot water and stirred at 90 C. with 1.5 parts of an aqueous NH, HgN

S0 11 HO 'S- Example 3 1.6-hexamethylene diamine solution the pH-value of which has been adjusted to about 6. A fine precipitate of an insoluble dyestuff salt is thus obtained. It is filtered off by suction, washed and extracted with boiling water. The yield amounts to 4.5 parts. The dyestutf gives blue dyeings of good fastness properties for example on wool and polyamide fibres which are superior to those of the dyeings obtained with the initial sulfonic acid which have not been reacted with an amine. The formula of the obtained dyestufif is:

47 parts of the sodium salt of l-amino-4-bromanthraquinone-Z-sulfonic acid, 10 parts of bis-(p-aminophenyl)- methane, 20 parts of anhydrous sodium carbonate and 2 parts of copper sulfate are heated in 800 parts of a mixture of equal parts of methanol and water for 24 hours at 75 C. while stirring. Then 20 parts of bis-(p-aminocyclohexyl)-methane are added thereto and the mixture is heated at 90 C. for about 1 hour further. After distilling off the alcohol and allowing to cool, the supernatant liquid is decanted off, and the remaining portion 0 Y n 0 is stirred with several portions of water while heating and i I neutralized with dilute hydrochloric acid. The dyestufi, after filtration by suction and washing, is extracted several times with boiling water for the purpose of purification, the dyestuff being previously comminuted by grind- H ing if desired. The yield amounts to 53 parts of the 0 NH-CBHFCHTOBHPNH 0 dyestutf obtained according to Example 2.

Example 6 A dilute solution of 2.5 parts of bis-(p-monomethylaminocyclohexyl)-methane in dilute hydrochloric acid which has a pH-value of about 6 to 7 is added to a solution of 10 parts of the dyestuff obtained by condensing 2 Example 4 3 parts of bis-(p-aminocyclohexyl)methane, dissolved in a little alcohol, are added to a solution of 5 parts of the sodium salt of the dyestuff obtained by condensing 2 mols of l-amino-4-bromanthraquinone-2-su1fonic acid and mols of l-amino-4-bromanthraquinone-2-su1fonic acid 1 mol of bis-(p-aminophenyl)-methane in hot Water and and 1 mol of 2.2-bis-(p-aminophenyl)-propane in 250 the mixture is kept for about 1 hour at a temperature parts of water. The whole is stirred for some time while of about 90 C. while stirring. The precipitated reaction being heated at 90 C. on the water bath and the excess product is filtered ofi by suction, washed with hot water of amine is neutralized with dilute hydrochloric acid. and again extracted with boiling water to which'a small The precipitated dye salt is filtered otf by suction and amount of the hydrochloric acid amine solution is added. washed. 5.5 parts of dyestutt are obtained, the dyeings 5.5 parts of an insoluble dyestutf are obtained which dyes, for example, wool or polyamide fibres greenish blue shades of good fastness properties which are superior to those of the dyeings obtained with the initial sulfonie acid which have not been reacted with an amine.

6 What we claim is: 1. Anthraquinone dyestuffs of the general formula Example 7 5 100 parts of polyamide fibres for example condensall liIH, tion products of hexamethylene diamine adipate or com 30,3 Hots densation products of E-amino caprolactame, are dyed at 98 to 100 C. for 60 minutes in a bath of 1 part of the 10 13888), dyestufi prepared according to Example 2 or 3, 4 parts of 30 percent ammonia, 4 parts of ammonium sulfate and l H i A 4 parts of the hydroxyethyl-ation product of 1 mol .of sperm oil alcohol and 24 mols of ethylene oxide in 2000 parts of water. A pure blue dyeing is obtained having y good light and Wet fastfless Pr p which are wherein X represents a bivalent radical selected from the Superior to those of the dyeing Obtamed with the initial group consisting of diphenyl methane and 2.2-diphenyldyestufi of Examples 2 and propane joined in the pand p'- positions of the benzene Example 8 nuclei with the NH- groups of the anthraquinone radi- 100 parts of a polyamide fabric for example condensacab, and represents an equivalent of 3 tion products f hexamethylene diamine adipate-or saturated dr-amlne selected from the group conslstmg of densation products of E-amino caprolactame, are dyed bis (py y -(P- Y for minutes at to c. in a bath containing fin cy y1)- bis-(ndimethylamin0cyc10- 2 parts of the dyestuflE according to Example 5, 10 parts hexyl)-methane and 1.6-hexamethy1ene diamine. of 30 percent ammonia and 10 parts of the hydroxyethyl- 25 2. The anthraquinone dyestutt of the formula 0 NH: HgN' (I) SO H H018 ONH SOgH HO;

0 HN-CdEh-CHr-C 3. The anthraquinone dyestufi of the formula where M: represents a methyl group.

4. The anthraquinone dyestuff of the formula liiaN' ation product of 1 mol of octadecanol and 25 mols of 60 5. The anthraquinone dyestufi of the formula ethylene oxide. 10 parts of ammonium sulfate are then added and the whole dyed for another 45 minutes at boiling temperature. A pure blue dyeing is obtained having very good fastness properties, especially outstanding wet fastness properties which are better than those of the dyeings obtained with the initial dyestufi of Example 5.

References Cited in the file of this patent UNITED STATES PATENTS 2,055,588 Pospiech Sept. 29, 1936 2,302,749 Dean Nov. 24, 1942 2,353,041 Klein July 4, 1944 2,705,717 Oppliger Apr. 5, 1955 Patent No. 2,913,465

November 1'7, 1959 Karl Meier et a1.

lines 6 12, inclusive, the left-hand portion of the appear aslf shown below inscead of as in the patent:

Column 6, formula should O PIN-- Signed and sealed this 7th day of June 1960.,

Attesi:

KARL AXLINE ROBERT C, WATSON Attesting Officer Commissioner of Patents 

1. ANTHRAQUINONE DYESTUFFS OF THE GENERAL FORMULA 